ANALYTICAL CHEMISTRY

FOR CHEMICAL TECHNOLOGY PROGRAM

EXERCISES AND PROBLEMS

(Semester 3/2023-2024)
 Chapter 1: Chemical Measurements
1. Define the following terms:
(a) Molarity
(b) Molality
(c) Density
(d) Weight percent
(e) Volume percent
(f) Parts per million
(g) Parts per billion
(h) Formal concentration
2. Any dilute aqueous solution has a density near 1.00 g/mL. Suppose the solution contains 1
ppm of solute; express the concentration of solute in g/L, mg/L, mg/mL, and mg/L.
3. The density of 70.5 wt% aqueous perchloric acid is 1.67 g/mL. Recall that grams refer to
grams of solution (5 g HClO4 1 g H2O).
(a) How many grams of solution are in 1.000 L?
(b) How many grams of HClO4 are in 1.000 L?
(c) How many moles of HClO4 are in 1.000 L?
4. How many milliliters of 3.00 M H2SO4 are required to react with 4.35 g of solid containing
23.2 wt% Ba(NO3)2 if the reaction is ?
5. Describe the preparation of:
a. 1.00 L of 0.0500 M KMnO4 from the solid reagent.
b. 1.00 L of 0.05 N H2C2O4, starting with an 1.00 M solution of the reagent.
c. 200 mL of 1.00 % (w/v) aqueous CuSO4 from the solid reagent CuSO4.5H2O.
d. 1 L of 0.100 M NaOH from the concentrated commercial reagent [50% NaOH (w/w),
specific gravity 1.525]
e. 1.00 L of a solution that is 12.0 ppm in K-, starting with solid K4[Fe(CN)6]
6. The amount of oxalic acid in a sample of rhubarb was determined by reacting with Fe3+ as
outlined in reaction:
2Fe3+(aq) + H2C2O4(aq) + 2H2O(l) → 2Fe2+(aq) + 2CO2(g) + 2H3O+(aq)
a. Describe how to prepare 250 mL of 0.0500 N Fe3+ (with 0.1 M H2SO4 to obtain a stock
solution from the solid reagent ammonium iron (III) sulfate dodecahydrate
(NH4Fe(SO4)2.12H2O, FM 482.19 g/mol).
b. In a typical analysis, the oxalic acid in 10.62 g of rhubarb was extracted with a suitable
solvent. The complete oxidation of the oxalic acid to CO2 required 20.10 mL of
0.0500 N Fe3+. What is the weight percent of oxalic acid in the sample of rhubarb?
Express the oxalic acid concentration in pg/g, μg/g, g/g, parts per million, and parts per
billion.
 Chapter 2: Tools of the Trade
7. A sample of ferric oxide (Fe2O3, density 5 5.24 g/mL) obtained from ignition of a
gravimetric precipitate weighed 0.296 1 g in the atmosphere. What is the true mass in
vacuum?
8. A stock solution contains 51.38 mmol KMnO4/L. How can you use pipets in Table 2-4 plus
a 100- or 250-mL volumetric flask to obtain approximately 1, 2, 3, and 4 mmol KMnO4/L?
What will be the exact concentrations of the solutions?

9.
a. How much of the primary standard benzoic acid (FM 122.12, density = 1.27 g/mL)
should you weigh out to obtain a 100.0 mM aqueous solution in a volume of 250 mL?
b. Serial dilution. You have available 5- and 10-mL transfer pipets plus volumetric fl asks
of the following sizes: 100, 250, 500, and 1 000 mL. Devise a serial dilution that will
give 50.0 mM benzoic acid.
 Chapter 3: Experimental Error
10. An empty crucible weighs 12.4372 g and the same crucible containing a precipitate from a
gravimetric analysis weighs 12.529 6 g.
(a) Each mass has six significant digits. What is the mass of precipitate contained in the
crucible and how many significant digits are in that mass?
(b) The manufacturer states that the balance has an uncertainty of 60.3 mg. Find the
absolute and relative uncertainty of the mass of the precipitate and write the mass with
a reasonable number of digits.
11. Write each answer with a reasonable number of figures. Find the absolute and percent
relative uncertainty for each answer.
(a) 12.41 (0.09) 4.16 (0.01)] x 7.0682 (0.0004) =?
(b) 3.26 (0.10) x 8.47 (0.05)] - 0.18 (0.06) =?
(c) 6.843 (0.008) x 104 [2.09 (0.04) - 1.63 (0.01)] =?
(d) = ?
(e) (3.24 0.08)4 =?
(f) log (3.24 0.08) =?
12. The pH of a solution is 4.44 0.04. Find and its absolute uncertainty?
13.
(a) How many milliliters of 53.4 (60.4) wt% NaOH with a density of 1.52 (60.01) g/mL
will you need to prepare 2.000 L of 0.169 M NaOH?
(b) If the uncertainty in delivering NaOH is 60.01 mL, calculate the absolute uncertainty
in the molarity (0.169 M). Assume there is negligible uncertainty in the formula mass
of NaOH and in the final volume (2.000 L).
14. Explain the difference between systematic and random error.
15. State whether the errors in (a)–(d) are random or systematic:
(a) A 25-mL transfer pipet consistently delivers 25.031 6 0.009 mL.
(b) A 10-mL burette consistently delivers 1.98 6 0.01 mL when drained from exactly 0 to
exactly 2 mL and consistently delivers 2.03 mL 6 0.02 mL when drained from 2 to 4
mL.
(c) A 10-mL burette delivered 1.983 9 g of water when drained from exactly 0.00 to 2.00
mL. The next time I delivered water from the 0.00 to the 2.00 mL mark, the delivered
mass was 1.990 0 g.
(d) Four consecutive 20.0-mL injections of a solution into a chromatograph were made
and the area of a particular peak was 4 383, 4 410, 4 401, and 4 390 units.
 Chapter 4: Statistics
16. For the numbers 116.0, 97.9, 114.2, 106.8, and 108.3, find the mean, standard deviation,
standard uncertainty (= standard deviation of the mean), range, and 90% confidence
interval for the mean. Using the Grubbs test, decide whether the number 97.9 should be
discarded.
17. Bicarbonate in replicate samples of horse blood was measured four times by each of two
methods with the following results:
Method 1: 31.40, 31.24, 31.18, 31.43 mM
Method 2: 30.70, 29.49, 30.01, 30.15 mM
(a) Find the mean, standard deviation, and standard uncertainty (= standard deviation of
the mean) for each analysis.
(b) Are the standard deviations significantly different at the 95% confidence level?
18. Traces of toxic, man-made hexachlorohexanes in North Sea sediments were extracted by a
known process and by two new procedures and measured by chromatography.
(a) Is the concentration pg/g parts per million, parts per billion, or something else?
(b) Is the standard deviation for procedure B significantly different from that of the
conventional procedure?
(c) Is the mean concentration found by procedure B significantly different from that of the
conventional procedure?
(d) Answer the same two questions as parts (b) and (c) to compare procedure A to the
conventional procedure.
Method Concentration found Standard deviation Number of
(pg/g) (pg/g) replications

Conventional 34.4 3.6 6

Procedure A 42.9 1.2 6
Procedure B 51.1 4.6 6
Source: Sterzenbach, B.W.Wenclawiak, and V.Weiglt, Anal, Chem. 1997, 69, 831
19. In the Bradford protein determination, the color of a dye changes from brown to blue when
it binds to protein. Absorbance of light is measured.
Protein (mg) 0.00 9.36 18.72 28.08 37.44
Absorbance at 595 nm 0.466 0.676 0.883 1.086 1.280
An unknown protein sample gave an absorbance of 0.973. Calculate the number of
micrograms of protein in the unknown and estimate its uncertainty.
20. Hydrocarbons in the cab of an automobile were measured during trips on the New Jersey
Turnpike and trips through the Lincoln Tunnel connecting New York and New Jersey. The
concentrations (6 standard deviations) of m- and p-xylene were:
Turnpike: 31.430.0mg/m3 (32 measurements)
 Tunnel: 52.9 29.8 mg/m3 (32 measurements)
Do these results differ at the 95% confidence level? At the 99% confidence level?
 Chapter 5: Quality Assurance and Calibration Methods
21. Internal standard.
A solution was prepared by mixing 5.00 mL of unknown element X with 2.00 mL of
solution containing 4.13 ug of standard element S per milliliter and diluting to 10.0 mL.
The signal ratio in atomic absorption spectrometry was (signal from X)/ (signal from S)
0.808. In a separate experiment, with equal concentrations of X and S, (signal from
X)/(signal from S) 1.31. Find the concentration of X in the unknown.
22. Standard addition graph. Tooth enamel consists mainly of the mineral calcium
hydroxyapatite, Ca10(PO4)6(OH)2. Trace elements in teeth of archeological specimens
provide anthropologists with clues about diet and diseases of ancient people. Students at
Hamline University used atomic absorption spectroscopy to measure strontium in enamel
from extracted wisdom teeth. Solutions were prepared with a constant total volume of 10.0
mL containing 0.750 mg of dissolved tooth enamel plus variable concentrations of added
Sr.
(a) Find the concentration of Sr and its uncertainty in the 10 mL sample solution in parts
per billion (ng/mL)
(b) Find the concentration of Sr in tooth enamel in parts per million (mg/g)
(c) If the standard addition intercept is the major source of uncertainty, find the
uncertainty in the concentration of Sr in tooth enamel in parts per million.
(d) Find the 95% confidence interval for Sr in tooth enamel.

23. Standard addition.

Lead in dry river sediment was extracted with 25 wt% HNO3 at 35oC for 1 h. Then 1.00 mL
of filtered extract was mixed with other reagents to bring the total volume to Vo = 4.60
mL.
Pb(II) was measured electrochemically with a series of standard additions of 2.50 ppm
Pb(II).
(a) Volume is not constant, so follow the procedure of Figures 5-5 and 5-6 (page107) to
find ppm Pb(II) in the 1.00-mL extract.
(b) Find the standard uncertainty and 95% confidence interval for the x-intercept of the
graph. Assuming that uncertainty in intercept is larger than other uncertainties,
estimate the uncertainty in ppm Pb(II) in the 1.00-mL extract.
Chapter 6: Chemical Equilibrium
24. Consider the following equilibria in aqueous solution:

a. Calculate the numerical value of the equilibrium constant for the reaction .
b. Calculate the concentration of AgCl(aq) in equilibrium with excess undissolved solid
AgCl.
c. Find the numerical value of K for the reaction
25. Which will be more soluble (moles of metal dissolved per liter of solution), Ba(IO3)2
(Ksp = 1.5 × 10-9) or Ca(IO3)2 (Ksp = 7.1 × 10-7)? Give an example of a chemical reaction
that might occur that would reverse the predicted solubilities.
26. Is it possible to precipitate 99.0% of 0.010M Ce3+ by adding oxalate ( without precipitating
0.0101 M

27. A solution contains 0.01 M Ba2+ and 0.010 M Ag+. Can 99% of Ca2+ be precipitated by
sulfate without precipitating Ag+? What will be the concentration of Ca2+ when Ag2SO4
begins to precipitate.
28. Given the following equilibria, calculate the concentration of each zinc species in a
solution saturated with Zn(OH)2 and containing at a fixed concentration of M.

29. Identify the conjugate acid – base pair in the following reactions:

30. Write the autoprotolysis reaction of H2SO4.

31. Calculate and pH for the following solutions:
(a) 0.010 M HNO3 (d) 3.0 M HCl
(b) 0.035 M KOH (e) 0.010 M
(c) 0.030 M HCl Tetramethylammonium hydroxide
32. From the Kb values for phosphate in equations 6-32 through 6-34, calculate the three Ka
values of phosphoric acid.
 Chapter 9: Monoprotic Acid-Base Equilibria
33. Why doesn’t water produce 10-7 M and 10-7 M when HBr is added?
34. Neglecting activity coefficients, calculate the pH of
(a) 1.0 x 10-3 M HBr;
(b) 1.0 x 10-2 M KOH.
35. Find the pH and fraction of dissociation (a) of a 0.100 M solution of the weak acid HA
with
.
36. A 0.045 0 M solution of benzoic acid has a pH of 2.78. Calculate pKa for this acid.
37. A 0.045 0 M solution of HA is 0.60% dissociated. Calculate pKa for this acid.
38. Barbituric acid dissociates as follows:
(a) Calculate the pH and fraction of dissociation of M barbituric acid.
(b) Calculate the pH and fraction of dissociation of M barbituric acid.
39. Find the pH and concentrations of and in a 0.060 M solution of trimethylamine.
40. Find the pH of 0.050 M NaCN
41. A 0.10 M solution of a base is 2.0% hydrolyzed (α = 0.020). Find Kb.
42. Describe how to prepare 250 mL of 1.00 M ammonia buffer, pH 9.00, starting with 28 wt%
NH3 (“concentrated ammonium hydroxide” listed on the back inside cover of the book) and
“concentrated” HCl (37.2 wt%) or “concentrated” NaOH (50.5 wt%).
43. A buffer was prepared by dissolving 0.100 mol of the weak acid HA () plus 0.050 mol of
its conjugate base Na+A- in 1.00 L. Find the pH.
44. Write the Henderson-Hasselbalch equation for a solution of formic acid. Calculate the
quotient at
(a) pH 3.000;
(b) pH 3.744;
(c) pH 4.000.
45. Calculate the pH of a solution prepared by mixing 0.080 0 mol of chloroacetic acid plus
0.040 0 mol of sodium chloroacetate in 1.00 L of water.
(a) First do the calculation by assuming that the concentrations of HA and A- equal their
formal concentrations.
(b) Then do the calculation, using the real values of [HA] and [A-] in the solution.
(c) Using first your head, and then the Henderson-Hasselbalch equation, find the pH of a
solution prepared by dissolving all the following compounds in one beaker containing
a total volume of 1.00 L: 0.180 mol ClCH2CO2H, 0.020 mol ClCH2CO2Na, 0.080 mol
HNO3, and 0.080 mol Ca(OH)2. Assume that Ca(OH)2 dissociates completely.
46. Consider the equilibria and calculate the pH of the following solutions
(a) HCl 0.01 M; HCl 2.10-8 M
(b) H2SO4 0.01 M; H2SO4 2.10-8 M
(c) CH3COOH 0.01 M; CH3COOH 2.10-8 M
(d) NH3 0.01 M; NH3 2.10-8 M
(e) KCN 0.02 M
(f) Na2CO3 0.05 M
(g) NaHCO3 0.01 M
 Chapter 10 Polyprotic Acid-Base Equilibria
47. How many grams of NaHCO3 (FM 84.01) must be added to 4.00 g of K2CO3 (FM 138.21)
to give a pH of 10.80 in 500 mL of water?
48. Consider the diprotic acid H2A with and . Find the pH and concentrations of , , and in:
(a) 0.100 M ;
(b) 0.100 M NaHA;
(c) 0.100 M Na2A.
49. How many grams of Na2CO3 (FM 105.99) should be mixed with 5.00 g of NaHCO3 (FM
84.01) to produce 100 mL of buffer with pH 10.00?
50. How many milliliters of 0.202 M NaOH should be added to 25.0 mL of 0.023 3 M salicylic
acid (2-hydroxybenzoic acid) to adjust the pH to 3.50?
51.
(a) Which two of the following compounds would you mix to make a buffer of pH 7.45:
H3PO4 (FM 98.00), NaH2PO4 (FM 119.98), Na2HPO4 (FM 141.96), and Na3PO4 (FM
163.94)?
(b) If you wanted to prepare 1.00 L of buffer with a total phosphate concentration of 0.050 0
M, how many grams of each of the two selected compounds would you mix together?
(c) If you did what you calculated in part (b), you would not get a pH of exactly 7.45.
Explain how you would really prepare this buffer in the lab.
 Chapter 11: Acid-Base Titrations
52. Consider the titration of 100.0 mL of 0.100 M NaOH with 1.00 M HBr. Find the pH at the
following volumes of acid added and make a graph of pH versus Va: Va = 0, 1, 5, 9, 9.9,
10, 10.1, and 12 mL.
53. A weak acid HA (pKa = 5.00) was titrated with 1.00 M KOH. The acid solution had a
volume of 100.0 mL and a molarity of 0.100 M. Find the pH at the following volumes of
base added and make a graph of pH versus Vb: Vb = 0, 1, 5, 9, 9.9, 10, 10.1, and 12 mL.
54. A 100.0-mL aliquot of 0.100 M weak base B (pKb = 5.00) was titrated with 1.00 M
HClO4. Find the pH at the following volumes of acid added and make a graph of pH versus
Va: Va = 0, 1, 5, 9, 9.9, 10, 10.1, and 12 mL.
55. The dibasic compound B (pKb1 = 4.00, pKb2 = 8.00) was titrated with 1.00 M HCl. The
initial solution of B was 0.100 M and had a volume of 100.0 mL. Find the pH at the
following volumes of acid added and make a graph of pH versus Va: Va = 0, 1, 5, 9, 10, 11,
15, 19, 20, and 22 mL.
56. A 100.0-mL aliquot of 0.100 M diprotic acid H2A (pK1 5 4.00, pK2 5 8.00) was titrated
with 1.00 M NaOH. Find the pH at the following volumes of base added and make a graph
of pH versus Vb: Vb = 0, 1, 5, 9, 10, 11, 15, 19, 20, and 22 mL.
57. Give the name and formula of a primary standard used to standardize (a) HCl and (b)
NaOH.
58. A solution was prepared from 1.023 g of the primary standard tris (Table 11-4) plus 99.367
g of water; 4.963 g of the solution were titrated with 5.262 g of aqueous HNO3 to reach the
methyl red end point. Calculate the concentration of the HNO3 (expressed as mol HNO3/kg
solution).